Deviation In Isentropic Compressibility Research Articles

Experimental and computational insight in molecular interactions of imidazolium based deep eutectic solvent with selected alcohols (C1 and C2)

The experimental thermophysical properties (densities (ρ), speed of sound (u) and refractive (nD) indices) of binary mixtures containing 1:3 mol ratio of [1-butyl-3-dimethylimidazolium chloride to ethylene glycol] [BMIM]Cl: EG], deep eutectic solvent (DES), with selected alcohols (methanol and ethanol) were measured. The measurements of the binary mixtures and the pure solvents were conducted at temperatures ranging from (293.15 to 313.15) K in the interval of 5 K and at ambient pressure using an Anton Paar densitometer. Thermodynamic properties such as excess molar volumes (VmE), intermolecular free length (Lf), isentropic compressibilities (ks), deviation in isentropic compressibilities (Δks) and deviation in refractive indices (ΔnD) were computed from the measured data of physical properties. These excess thermodynamic properties are utilized to investigate the intermolecular interactions occurring between imidazolium DES and methanol or ethanol. Geometry optimization calculations were undertaken using Density Functional Theory (DFT) to model the structure of DES with a 1:1 mol ratio employing the B3LYP-D3 functional and a basis set of 6–31G++**. The DFT results revealed that the interaction energies within the DES in the presence of solvent favoured the formation of the complex. Furthermore, interrogation of the optimized structures at molecular level showed that the interactions were mediated by the electrostatic ionic bonding with the co-solvent playing a significant role in solubility. The excess molar volumes of binary mixtures were correlated using the Lorentz-Lorenz equation, and the densities and refractive indices were predicted using the Lorentz-Lorenz equation. The interaction energies and electrostatic interactions between the different solvents were predicted using quantum mechanics. The experimental data was found to be in good agreement with the theoretical data for the measured properties as well as the computational predictions of the stability of the systems.

The study of thermodynamic properties of diethylene glycol monoethyl ether with 2-alkanols (C3 − C7) with use of PFP and ERAS modeling

Thermodynamic properties like excess volume VmE, excess partial volume V¯m,iE, in isentropic compressibility deviations Δ Ks, and refractive index deviations ΔnD, have been calculated based on experimental density ρ, speed of sound u, and refractive index nD, by an Anton Paar / DSA 5000/ densimeter and Anton Paar Abbemat / 500/ refractometer. The systems of diethylene glycol monoethyl ether (DEGEE) + 2-propanol, or + 2-butanol, or + 2-pentanol, or + 2-hexanol, or + 2-heptanol, were given at T = (298.15–318.15) in 10 K intervals at ambient pressure (81.5 kPa) have been investigated. Data was fitted by Redlich-Kister relation.TheVmE is negative for + 2-propanol and positive sign for other systems observed. The Δ Ks is negative for all systems, except for + 2-heptanol system is positive. The ΔnD is negative for + 2-hexanol or + 2-heptanol systems and is positive for all the rest. The The intermolecular interactions and structure factors were discussed for the binary mixtures. In addition the Prigogine–Flory–Patterson theory (PFP) and Extended Real Associated Solutions (ERAS) models were used to correlate VmE data of binary mixtures. The fitting data for all systems reasonable consistency with experimental data for all the systems.

Ultrasonic Velocity of Acrylates with Decane-2-ol at 313.15 K

Thermodynamic data involving ultrasonic velocities of binary liquid mixtures of methyl acrylate, ethyl acrylate and butyl acrylate with decane-2-ol have been measured at 313.15 K and at atmospheric pressure. Study of thermodynamic properties involves challenges of interpreting the excess quantities as a means of understanding the nature of intermolecular interactions among the mixed components. Experimental values of ultrasonic velocities were correlated with recently proposed Jouyban-Acree model. Deviations in isentropic compressibility were calculated and have been fitted to Redlich-Kister polynomial equation. Excess parameters like specific acoustic impendence, intermolecular free length, available volume, intrinsic pressure, molecular association and molar sound velocity were also calculated. Graphical representations of excess derived thermodynamic parameters used to explain the type and extent of intermolecular interactions

Application of PC‐SAFT EoS and SCFT for the modeling of thermophysical properties comprising deep eutectic solvent and alcohols

AbstractZinc (II) chloride based deep eutectic solvent (DES) were formed by mixing zinc (II) chloride with phosphoric acid. Fourier‐transform infrared spectroscopy was used to identify any possible shifts when the two compounds were assorted, and differential scanning calorimetry (SDT Q600 V20.9 Build 2D) was utilized to evaluate the formation of deep eutectic solvent. Densities, , and speed of sound, u, of [ZnCl2][phosphoric acid] 1:2.5 with methanol, ethanol, or propanol have been measured at T = (293.15, 303.15, 308.15, and 313.15) K and at atmospheric pressure. Excess molar volumes ( ), isentropic compressibilities ( ), deviation in isentropic compressibility ( ), and intermolecular free length ( ) were calculated from the densities, and speed of sound, respectively. To fit the excess molar volumes and deviation in isentropic compressibilities, the Redlich–Kister smoothing polynomial was used. Also, we have used perturbed chain statistical associating fluid theory equation of state (PC‐SAFT EoS) for modeling the densities of the binary mixtures, and Schaaff's collision factor theory (SCFT) and Nomoto's relation (NR) were used for modeling the speed of sounds for the binary mixtures.

Thermodynamic properties of P-methyl acetophenone with cyclohexylamine, cyclohexanol, and cyclohexane at various temperatures (strong and weak interactions)

ABSTRACT The density, viscosity and sound velocity of the binary liquid mixtures of P-methyl acetophenone with cyclohexylamine, cyclohexanol, and cyclohexane are measured over the complete composition range at temperatures of 303.15–313.15 K and at atmospheric pressure of 0.1 M. Excess molar volume, excess isentropic compressibility and viscosity deviation are calculated from the experimental measurements. The sign and magnitude of the derived parameters reveal the nature and type of interactions between the constituent molecules in the binary mixtures. Thermodynamic properties for this work reveal association interactions between dissimilar molecules in the binary systems P-methyl acetophenone + cyclohexylamine and P-methyl acetophenone + cyclohexanol systems, whereas dispersion forces cause the opposite trend in the other binary system P-methyl acetophenone + cyclohexane.

Excess Properties, Partial Volume per Mole and FITR Spectral Studies in Liquid Mixtures of Furfuryl Alcohol with Primary and Secondary Anilines

ABSTRACT Speeds of ultrasound and densities of Furfuryl alcohol (FFA), Aniline (AN), N-Methylaniline (NMA) and N-Ethylaniline (NEA) along with the binary mixtures FFA+AN, FFA+NMA, FFA+NEA are measured at temperatures (303.15–318.15) K. From the experimental speed of ultrasound and density, excess parameters namely excess intermolecular free length ( L f E ), excess volume per mole ( V m E ) and deviation in isentropic compressibility (∆κs) are determined. The result of excess properties is supported by excess partial volume per mole ( V ˉ m , i E ) studies. The calculated excess and deviation functions have been fitted to the Redlich-Kister polynomial equation, and the observations have been analysed in terms of molecular associations. The variation of these excess parameters indicated the presence of specific interactions between component molecules. Further, FTIR spectra for the three mixtures were recorded and analysed to correlate with the thermodynamic and volumetric results. A good agreement was found between the two studies.

Molecular interactions between 2-methyltetrahydrofuran and alcohols: A combination of thermodynamic, spectroscopic and quantum chemistry studies

New data of density (ρ), viscosity (η), and speed of sound (u) have been determined at T = (288.15–303.15 K) and p = 93.2 kPa for the binary mixture of {2-methyltetrahydrofuran + ethanol, or + 1-propanol, or + 1-butanol, or + 1-pentanol} over the entire composition range. These results were used to calculate the excess molar volume (VmE), isentropic compressibility deviation (Δκs), viscosity deviation (Δη), and Gibbs excess activation energy (ΔG*E), which were correlated by a Redlich-Kister polynomial. For all systems studied, the values ​​of the deviation properties were negative, which probably indicates a predominance of structural and chemical effects over physical effects. Five viscosity models were employed to fit the viscosity data. The VmE data were also correlated by the Prigogine-Flory-Patterson Theory (PFP Theory) and the Peng-Robinson-Stryjek-Vera Equation of State (PRSV EOS). Furthermore, a Fourier Transform Infrared (FT-IR) spectroscopy study was performed to explain the hydrogen bonding interactions. Lastly, theoretical calculations using Density Functional Theory (DFT) at B3LYP-GD3(BJ)/6–311++G(3df,2p) level of theory were performed to understand the inter-interactions between the compounds present in the mixtures. The FT-IR and computational results were in good agreement with the experimental data.

Application of ERAS-model and PFP theory on excess and deviation properties for binary systems of ionic liquid + amine derivatives

Thermodynamics of mixtures includes ionic liquid 2-hydroxyethylammonium propionate [2-HEAPr] + 1-propanol, 3-amino-1-propanol [AP], 1-amino-2-propanol [MIPA], and monoethanolamine [MEA] were studied. Density ρ, speed of sound u, and refractive index nD of pure and mixtures were measured at T = (298.15, 308.15, 318.15) K. Excess molar volume VmE, excess partial molar volume Vm,iE, excess thermal expansion coefficient αE, isothermal coefficient of excess molar enthalpy (∂Hm∂P)T,x, deviations in isentropic compressibility Δ ks, and refractive index Δ nD were calculated and data correlated with Redlich-Kister polynomial relation. The Prigogine-Flory-Patterson (PFP) and Extended Real Associated Solution (ERAS) models were applied to analyze intramolecular and intermolecular interactions between like and unlike molecules. The accuracy of theoretical models were found to be in agreement with empirical results. Finally, the study confirmed the structures of the ILs using FT-IR and HNMR analysis.

Thermodynamic study of mesitylene + alkanol mixtures: Insights into molecular interactions

Excess properties are a powerful tool for understanding the intermolecular interactions in mixtures. In this study, the excess molar volume (VmE), excess isentropic compressibility (κsE) deviation in ultrasonic speed (Δu), and refractive index (ΔnD) were analyzed for mixtures of mesitylene and alkanol to interpret their intermolecular interactions. Our findings demonstrate that positive values of VmE and κsE indicate the predominance of the rupture of H-bonding in self-associated alkanol dominate over the electron donor–acceptor interaction between the hydroxyl group of alkanol and π–electrons of mesitylene. It was also observed that these electron donor–acceptor interactions weaken as the temperature increases. These observations were further supported by the behavior of molecular association parameter (MA), free intermolecular length, and available volume. Among the alkanols studied, n-butanol exhibited the highest value of MA, suggesting a strong degree of molecular association due to favorable intermolecular interactions between the dissimilar molecules. In contrast, sec-butanol showed the lowest value, which can be attributed to the steric hindrance caused by three methyl groups of mesitylene and the two methyl groups attached to a hydroxyl carbon atom in sec-butanol. Regarding correlation, Schaffs collision factor theory demonstrated high predictive power for ultrasonic speed compared to other models.

Thermodynamic study of triacetin or ethyl levulinate and alcohol binary mixtures

The subject of presented research is the study of liquid binary mixtures consisting of ester and alcohol combination; triacetin or ethyl levulinate, as one component, and ethanol or isobutanol, as second component. Thermodynamic and transport data were measured in the broad temperature range, T=(288.15/298.15–323.15/333.15) K, and at atmospheric pressure, p = 0.1 MPa. All corresponding excess and deviation properties were calculated including the excess molar volume, viscosity deviation, refractive index deviation, isentropic compressibility deviation and excess molar Gibbs energy of activation of viscous flow, and correlated with the basic Redlich-Kister equation. The analysis of possible chemical interactions and structural effects taking place in the mixtures was led in the terms of ester structure, complexity of ester molecule and chain length and branching of the alcohol molecule. The thermodynamic analyses showed change of the sign of the excess molar volume depending on the alcohol present in the mixture. FT-IR spectra were recorded for all four systems for the compositions where maximum excess molar volumes are obtained to support the conclusions derived from the mixtures’ nonideal behaviour. In addition, modelling of viscosity is performed with the two- and three-parameter correlative models, as well as excess molar volume correlation with the Peng-Robinson equation of state and three-parameter van der Waals mixing rule.

Volumetric properties of binary liquid mixture of cyclopentyl methyl ether with 1-pentanol at 298.15 k temperature

The densities (ρ) and ultrasonic speeds (u) of Cyclopentyl methyl ether, 1- Pentanol and their binary mixture with the whole composition range have been measured at 298.15 K. From the experimental data the excess molar volume (VE), deviations in isentropic compressibility (∆ks), deviations in ultrasonic speed (∆u), deviations in acoustic impedance (∆Z) have been determined. The sign and magnitude of these parameters were found to be sensitive towards interactions prevailing in the studied system. Moreover, VE values were theoretically predicted by using Flory’s statistical theory. The variations of derived parameters mentioned above with composition offer a convenient method to study the nature and extent of interactions between the component molecules of the liquid mixture not easily obtained by other means.

Thermodynamic properties of binary liquid mixtures of benzyl alcohol with 2-Alkoxyethanols at varying temperatures

In the present research, density (ρ) and speed of sound (u) for binary liquid mixtures of the benzyl alcohol (BA) with three 2-alkoxyalcohols {2-methoxyethanol (2-ME), 2-ethoxyethanol (2-EE), and 2-butoxyethanol (2-BE)} at temperatures of 298.15, 303,15 and 308.15 K have been measured over complete concentration of benzyl alcohol under 0.1 MPa pressure. According to measured results, excess molar volume (VmE) and deviation in isentropic compressibility (Δκs) were computed and these observed results were correlated to Redlich−Kister (R-K) polynomial expansion. Further, molar volume (Vm), apparent molar volumes (Vm,∅,1 and Vm,∅,2), acoustic impedance (Z), isentropic compressibility (ks), intermolecular free length (Lf), deviation in intermolecular free length (ΔLf) were calculated at all worked temperatures. For all studied systems, excess molar volume (VmE) and deviation in isentropic compressibility (Δκs), and deviation in intermolecular free length (ΔLf) were negative over the entire mole fraction range of benzyl alcohol at all measured temperatures. Among the three systems, benzyl alcohol with 2-ethoxyethanol containing system showed more negative. By using the obtained results, intermolecular interactions were discussed between benzyl alcohol and 2-alkoxyethanols. Moreover, the influence of temperature on intermolecular interactions was analyzed using above said parameters.

Thermodynamic Properties of Binary Liquid Mixtures Containing Furfural with Chlorobenzene, Nitromethane, Diethylmalonate and 1-Butanol at 308.15K and 318.15K Supported by FTIR Spectral Studies

A study on thermodynamic properties of the liquid mixture is used in the industrial process, which often extends to solution chemistry. Density(ρ), Viscosity(η), and Ultrasonic velocity(U) were determined for binary liquid mixtures of furfural with chlorobenzene, nitromethane, diethyl malonate and 1- butanol at temperature of 308.15K and 318.15K at atmospheric pressure over the whole range of mole fractions. The calculated thermodynamic properties and some excess parameters such as Excess Volume(VE), Deviation in Isentropic Compressibility(∆KS), Deviation in Viscosity(∆η), Deviation in Intermolecular Free Length(∆LF), Deviation in Intermolecular Free Volume(∆VF), Deviation in Internal Pressure(∆π) and Deviation in Acoustic Impedance(∆Z) were calculated and applied to the Redlich-Kister type polynomial equation to determine the appropriate coefficients. The effects of composition and temperature on thermodynamic parameters have been studied in terms of molecule interaction in these liquid mixtures. Further, IR spectra of these liquid mixtures were recorded and the data were utilized to examine the mixing behavior of the components.

Molecular interactions of (ionic liquid butylammonium methanoate + alcohols) at several temperatures. Part II: sec-Butylammonium methanoate (S4Met)

Volumetric and acoustic properties were obtained by density (ρ) and speed of sound (u) experimental values for the binary liquid systems containing the protic ionic liquid (IL) sec-butylammonium methanoate (S4Met) + alcohols (ethanol, 1-propanol, 1-butanol and 1-pentanol) over the whole composition range at different temperatures (293.15–313.15) K and ambient pressure (p = 92.3 kPa). A neutralization reaction was carried out under controlled temperature to synthesize S4Met, which underwent spectroscopic analyses to guarantee its formation. All the excess properties, namely excess molar volume,VmE, excess partial molar volumes,V¯iE, and deviation in isentropic compressibility,ΔκS, presented negative values. Other volumetric properties such as partial molar volumes,V¯i, apparent molar volumes, Vϕi and infinite dilution volumes,V¯i∞, were determined. In addition to the thermodynamic approach, spectroscopy techniques essentially 1H NMR, 13C NMR, FTIR were useful in order to elucidate intermolecular interactions among the species in solutions. Lastly, the Peng-Robinson-Stryjek-Vera equation of state (PRSV EOS) was used to correlate the excess molar volumes.

The mixing properties, IR analysis and quantum chemical calculations of trimethoxylsilane derivatives with ethanol, 1-butanol, 1-pentanol and 1-octanol

The density, viscosity and speed of sound of trimethoxylsilane derivatives with ethanol, 1-butanol, 1-pentanol and 1-octanol have been measured at 298.15, 303.15, 308.15, 313.15 K, 318.15 and 323.15 K, respectively. The excess molar volume, viscosity deviation, excess Gibbs energy of activation of viscous flow, isobaric thermal expansivity and isentropic compressibility deviation were calculated from these results. The Redlich–Kister equation was used for the correlation. The calculated excess properties have been discussed according to the possible interactions formed between the molecules in the mixture using equimolar attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy. In all of the compositions and experimental temperature ranges studied, the excess molar volumes were found to be negative for vinyl trimethoxy silane and phenyl trimethoxy silane with ethanol. This may be attributed to the close accumulation of molecules and easier formation of cross-association structures between the alkoxysilane molecules. However, the excess molar volume of the binary mixture of vinyl trimethoxy silane and phenyl trimethoxy silane with n-butanol, n-pentanol, and n-octanol was positive. Hydrogen bond fracture may play a leading role in this process. The excess molar volumes of the binary system comprised of trifluoropropyl trimethoxy silane with ethanol and 1-octanol were all positive. This may be attributed to the influence of steric hindrance, which makes it difficult for trifluoropropyl trimethoxy silane to form a cross-association structure with alcohol molecules.

Influence of water and ethanol in the physical properties of choline glycinate at several temperatures

In this study, a physical characterization (density (ρ), refractive index (nD), speed of sound (u) and dynamic viscosity (η)) as a function of temperature (298.15–343.15 K) of choline glycinate (ChGly) and its binary mixtures with water or/and methanol over the entire composition range was performed from 298.15 K to 323.15 K. Several derived properties of the pure ionic liquid and excess molar volume (VmE) changes of refractive index on mixing (ΔnD), deviations in isentropic compressibility (ΔκS) and viscosity deviations (Δη) have been calculated using the experimental data in the selected temperature range. These experimental data of ChGly have been positively correlated using polynomial equations and the derived magnitudes were successfully fitted to Redlich-Kister equation. Finally, different models have been implemented for the first time to predict the density of the selected binary mixtures as a function of the temperature.

Densities and Sound Speeds of Ternary Mixtures Methyl tert-Butyl Ether + Toluene + n-Hexane (or Cyclohexane) and Their Binary Subsystems at a Temperature of 298.15 K and under Ambient Pressure

Densities ρ and sound speeds c of the ternary systems methyl tert-butyl ether (MTBE) + toluene + n-hexane, MTBE + toluene + cyclohexane, and related binary subsystems MTBE + toluene, MTBE + n-hexane, toluene + n-hexane, MTBE + cyclohexane, and toluene + cyclohexane are measured over the whole composition range at 298.15 K and under ambient pressure. The excess molar volumes, VmE, and isentropic compressibility deviations, ΔκS, were derived from experimental ρ and c data. The experimental results are discussed in terms of the possible interactions between molecules in the mixture and structural effects. The VmE and ΔκS data for the binary and ternary systems were correlated with the Redlich–Kister and Cibulka equations, respectively. Further, the ternary VmE and ΔκS data are compared with the predicted values using the binary contribution models of Radojković, Kohler, Rastogi, Tsao-Smith, Toop, and Scatchard. The root-mean-squared deviation between experimental and predicted values is used as a tool to measure the predicting capabilities of the tested models.

Volumetric, acoustic and viscometric properties of binary mixtures containing acetonitrile with glycols at several temperatures: Experimental study and correlations

Density, speed of sound and viscosity of binary mixtures of {acetonitrile + ethylene glycol (EG), or + diethylene glycol (DEG), or + triethylene glycol (TEG)} have been measured as a function of compositions at temperatures of 288.15, 293.15, 298.15 and 303.15 K and under atmospheric pressure. Excess molar volume, partial molar volume, excess partial molar volume, deviation in isentropic compressibility and deviation in viscosity were determined and excess properties have been fitted to the Redlich-Kister equation. The empirical models developed by Grünberg-Nissan, Heric-Brewer, Katti-Chaudhary and Van der Wyk were used to correlate the experimental viscosity data. The excess molar volume was also used to test the applicability of the Peng-Robinson-Stryjek-Vera equation of state (PRSV EOS).

A study on mixing properties of binary mixtures of 1-hexene with alkoxyethanols at different temperatures

Blends of 1-hexene with alkoxyethanols have been studied in terms of intermolecular interactions. The investigated alkoxyethanols were 2-methoxyethanol or 2-ethoxyethanol or 2-butoxyethanol. This study was based on measurements of densities, ρ, speeds of sound, u, and refractive indices, nD, throughout the full range of composition. With the help of measured data, some derived/excess properties have been computed such as excess molar volume, VmE, isentropic compressibility,κs, deviation in isentropic compressibility, Δκs, and deviation in refractive indices, ΔnD and these properties were fitted to a Redlich−Kister equation. Furthermore, PC-SAFT equation of state (PC-SAFT EoS) were used to correctly modeled the density of pure fluids and mixtures whereas the Nomoto’s relation modeled the speed of sound for the binary mixtures with the least deviation, while for the refractive index of all the mixtures, Laplace mixing rule was the best approach..

Excess Thermodynamic Properties of Ethyl Acetate with Primary Alcohols At 303.15 K

Densities (ρ) and sound velocity (u) for the binary mixtures of ethyl acetate with 1-methanol, 1- ethanol, 1- propanol, 1- butanol, 1-hexanol and 1-octanol were measured over the entire composition range at 303.15 K. From these data, excess molar volume (VE), isentropic compressibility (Ks ) and deviation in isentropic compressibility (ΔKs ) have been calculated with the Redlich-Kister Polynomial equation. The experimental data were discussed in terms of intermolecular interactions between component molecules.